Effect of isopropyl side chain branching and different anions on electronic structure, vibrational spectra, and hydrogen bonding of isopropyl-imidazolium-based ionic liquids: Experimental and theoretical investigations.

In the present work, four branched methylated, 1,2-dimethyl-3-isopropyl-imidazolium (i-[C3Dmim+]) and protonated,1-methyl-3-isopropyl-imidazolium (i-[C3mim+])-based ionic liquids (ILs) with varying anion (Br-, BF4-, PF6-, and NTf2-) were synthesized and investigated by NMR, infrared (IR) and Raman spectroscopy. Based on infrared and Raman spectroscopy, complete vibrational assignments have been performed. The IR and Raman analysis revealed that the vibrational spectra are virtually unaffected upon methylation, while significant frequency changes were observed by changing anion. Furthermore, to determine the electronic structure, energetic stability, and vibrational properties of these i-[C3Dmim]Y, i-[C3mim]Y (Y = Br, BF4, PF6, and NTf2) ion pairs, quantum chemical calculations including the dispersion correction method are performed both on single ions and on ionic couples. The calculated electron density was analyzed to expose non-covalent intra- and interionic interactions by the quantum theory of atoms in molecules (AIM) and interpreted in terms of both anion dependence and type of interaction. Computational results suggest that for all ionic couples the most energetically stable configuration is obtained with the anions located close to the C2 position of the imidazolium cation. However, in the case of i-[C3mim]NTf2 and i-[C3Dmim]BF4, similar energies were obtained in configurations 2 and 3 where the anion is located above the imidazolium ring. For i-[C3mim]Br a stronger hydrogen bond is predicted than for other studied ILs. Calculations indicate that a red shift of the CH stretching bands should occur due to hydrogen bonding; indeed, such displacement of bands is experimentally observed.

Decreasing toxicity and increasing photoconversion efficiency by Sn-substitution of Pb in 5-ammonium valeric acid-based two-dimensional hybrid perovskite materials.

The toxicity of Pb in halide-based hybrid perovskite materials stands in the way of their more extensive use, despite their excellent optical properties, high stability and very good photoconversion efficiency. The presented work focuses on addressing the toxicity issues in 2D perovskites. We use 5-ammonium valeric acid (AVA) as an organic spacer and partially or completely eliminate Pb by Sn and apply first principles-based density functional theory (DFT) calculations to determine the properties of these systems. Structural insights are gained, which predict the major changes in the inorganic framework including the metal-halide bond length and the bridging angle between two octahedral configurations. The replacement of Pb by Sn leads to a drastic reduction of the electronic band gap from 1.84 to 1.04 eV. Increasing the Sn content results in Sn-I bonds being stronger than the Pb-I bonds, which entails strong s-p coupling. The calculated effective masses of excitons decrease by up to ∼23% in the case of lead-free perovskites, which can be attributed to the more dispersive band edges due to stronger s-p coupling. The reduction of the effective masses of the charge carriers and the electronic band gap results in high electrical conductivity for the AVA2(MA)Sn2I7 2D perovskite structure. The three structures compared, where AVA2(MA)XI7 (X = Pb2, PbSn, Sn2) exhibit excellent thermoelectric power factors, which suggests promising applications for heat energy conversion. Moving toward lead-free 2D perovskites, the real part of the dielectric constants enhances, which may limit the radiative recombination of charge carriers. Furthermore, reducing the bandgap values by the substitution of Sn results in a red-shift in the edge of the absorption coefficients. Using the spectroscopic limited maximum efficiency (SLME) model, the best efficiencies of 32.20 and 30.08% are achieved for the AVA2(MA)PbSnI7 and AVA2(MA)Sn2I7 structures. The comparison of all three structures demonstrates that lead-free 2D perovskites are very good candidates for highly efficient solar energy conversion.

Glucose-induced self-assembly and phase separation in hydrophilic triblock copolymers and the governing mechanism.

Poly(ethylene oxide, EO)-poly(propylene oxide, PO)-poly(ethylene oxide, EO)-based triblock copolymers (BCPs) with 80% hydrophilicity stay molecularly dissolved as Gaussian chains at ambient temperature, even at fairly high concentrations (>5 %w/v). This study presents the plausible micellization behaviour of such very-hydrophilic Pluronics® - F38, F68, F88, F98, and F108 - incited upon the addition of glucose at low concentrations and temperatures. The outcomes obtained from phase behaviour and scattering studies are described. At temperatures near to ambient temperature, these BCPs form micelles with a central core made of a PO block, surrounded by a corona of highly hydrated EO chains. The phase transitions in these hydrophilic Pluronics® in the presence of glucose are demonstrated via the dehydration of the copolymer coil, leading to a decrease in the I1/I3 ratio, as determined using fluorescence spectroscopy. The temperature-dependent cloud point (CP) showed a marked decrease with an increase in the PO molecular weight and also in the presence of glucose. The change in solution relative viscosity (ηrel) caused by glucose is due to the enhanced dehydration of the EO block of the BCP amphiphile. Dynamic light scattering (DLS) and small-angle neutron scattering (SANS) investigations suggested that the dimensions of the hydrophobic core increase during the dehydration of the EO-PO blocks upon a temperature increase or after adding varying concentrations of glucose, thereby resulting in a micellar shape transition. It has been observed that added glucose influences the phase behaviour of BCPs in an analogous way to the influence of temperature. Also, plausible interactions between the EO-PO blocks and glucose were suggested based on the evaluated optimized descriptors obtained from a computational simulation approach. In addition, the core-shell blended micelles obtained using these BCPs are successfully utilized for drug (curcumin, Cur) solubilization based on the observed peak intensities from UV-visible spectroscopy. The loading of Cur into glucose-containing and glucose-free hydrophilic Pluronic® micelles shows how the radius of the micellar core (Rc) increases in the presence of glucose, thereby indicating Cur solubility enhancement for the Pluronic® micelles. Various kinetics models were employed, demonstrating a drug release profile that enables this approach to be used as an ideal platform for drug delivery.

Strong-field ionization of CH3Cl: proton migration and association.

Strong-field ionization of CH3Cl using femtosecond laser pulses, and the subsequent two-body dissociation of CH3Cl2+ along Hn+ (n = 1-3) and HCl+ forming pathways, have been experimentally studied in a home-built COLTRIMS (cold target recoil ion momentum spectrometer) setup. The single ionization rate of CH3Cl was obtained experimentally by varying the laser intensity from 1.6 × 1013 W cm-2 to 2.4 × 1014 W cm-2 and fitted with the rate obtained using the MO-ADK model. Additionally, the yield of Hn+ ions resulting from the dissociation of all charge states of CH3Cl was determined as a function of intensity and pulse duration (and chirp). Next, we identified four two-body breakup pathways of CH3Cl2+, which are H+ + CH2Cl+, H2+ + CHCl+, H3+ + CCl+, and CH2+ + HCl+, using photoion-photoion coincidence. The yields of the four pathways were found to decrease on increasing the intensity from I = 4.2 × 1013 W cm-2 to 2I = 8.5 × 1013 W cm-2, which was attributed to enhanced ionization of the dication before it can dissociate. As a function of pulse duration (and chirp), the Hn+ forming pathways were suppressed, while the HCl+ forming pathway was enhanced. To understand the excited state dynamics of the CH3Cl dication, which controls the outcome of dissociation, we obtained the total kinetic energy release distributions of the pathways and the two-dimensional coincidence momentum images and angular distributions of the fragments. We inferred that the Hn+ forming pathways originate from the dissociation of CH3Cl dications from weakly attractive metastable excited states having a long dissociation time, while for the HCl+ forming pathway, the dication dissociates from repulsive states and therefore, undergoes rapid dissociation. Finally, quantum chemical calculations have been performed to understand the intramolecular proton migration and dissociation of the CH3Cl dication along the pathways mentioned above. Our study explains the mechanism of Hn+ and HCl+ formation and confirms that intensity and pulse duration can serve as parameters to influence the excited state dynamics and hence, the outcome of the two-body dissociation of CH3Cl2+.

Mobility driven thermoelectric and optical properties of two-dimensional halide-based hybrid perovskites: impact of organic cation rotation.

The pivotal impact of organic cation rotation may result in structural complexity in two-dimensional (2D) halide-based hybrid perovskites. The crucial role of the orientation of the organic cation (MA = CH3NH3+) in the 2D Ruddlesden-Popper phase (2DRP) is explored using density functional theory (DFT) calculations. Our results propose that the MA cation rotation imposes the structural distortion in the PbI6 network, which is further responsible for the changes in nature and value of the electronic bandgap, charge density and optical absorption. The spin-orbit coupling effect results in a wide range of Rashba splitting parameters being obtained from 0.04 to 0.278 eV Å. The simulated optical absorption spectra suggest that absorption edge for the alignment of the MA molecule along the X-axis (having unidirectional hydrogen bonds) is higher than that of the alignment of the MA cation in the z-direction. Furthermore, the unidirectional hydrogen bonds between the MA cation and Pb-I framework significantly help to achieve the highest mobility of charge carriers up to ∼1437 cm2 V-1 s-1. Such high mobility leads to supremacy in the thermoelectric transport properties, which are investigated for the first time with the rotation of the MA cation. The calculated thermoelectric power factor at room temperature shows exceptionally high values (up to 2.04 mW m-1 K-2), leading to desired applications in thermoelectric devices. The rotation of the MA cation might be utilized as a useful tool for variation in optical absorption and transport coefficients. Therefore, our results spark the idea to develop 2D perovskites for real-time perspective in solar and heat energy utilization.

Improvement in metal vapor laser performance with reduction in localized electric field at electrodes.

Electrode geometry plays a vital role in metal vapor laser performance. It has been observed that by modifying the electrode geometry, the electric field enhancement near the electrode can be reduced. Reduction in the localized electric field causes reduction in the phantom current in the metal vapor laser. On replacing the electrode geometry having eight pins with an electrode having the zero-pin configuration, a 10% decrease in the phantom current and a 23% increase in optical output power are observed. The low phantom current is responsible for higher efficiencies, large specific average output power, and improved beam characteristics of that laser in reference to a conventional copper vapor laser. It was also observed that reduction in field enhancement causes reduction in the thermal loading at the cathode fall and in the probability of thermal instability, thereby improving the discharge stability and jitter in metal vapor lasers. This simple and effective technique can also be applied to the systems requiring high current and high-volume stable discharge.

A comprehensive multidisciplinary investigation on CO2 capture from diesel engine.

Climate change and global warming are the visible consequences of the increased amount of carbon dioxide (CO2) in the atmosphere. Among the various sources of anthropogenic CO2 emission, the diesel engine has a significant contribution. The development of a reliable system to efficiently minimize CO2 emissions from diesel engines to the safest level is lacking in the open literature. Therefore, a comprehensive multidisciplinary approach has been applied in this paper to investigate the efficacy of the post-combustion carbon capture (PCC) process for the diesel engine. The experiments have been performed on the exhaust of a direct injection diesel engine at five different brake powers with blends of aqueous ammonia (AQ_NH3), monoethanolamine (MEA), N,N-dimethylethanolamine (DMEA), and 1-ethyl-3-methylimidazolium tetrafluoroborate (C2mim BF4) ionic liquid (IL) as an absorbent for CO2 capture. The reaction mechanism of these absorbent with CO2 are also studied by the geometrical, energetical, MESP, frontier molecular orbitals, and NBO analysis using the first-principles density functional theory (DFT) calculations. The maximum CO2 absorption efficiency of almost 97% was achieved for the blend consisting of 67% of AQ_NH3 and 33% of MEA. Moreover, AQ_MEA and blend of AQ_NH3, DMEA, and C2mim BF4 ionic liquid showed 96% and 94% CO2 absorption efficiency, respectively.

Sequential and cellular detection of copper and lactic acid by disaggregation and reaggregation of the fluorescent panchromatic fibres of an acylthiourea based sensor.

We report, for the first time, the self-assembly of an acyl-thiourea based sensor, N-{(6-methoxy-pyridine-2-yl) carbamothioyl}benzamide (NG1), with panchromatic fluorescent fibres and its dual-sensing properties for the sequential detection of Cu2+ ions and lactic acid. The panchromatic fibres formed by NG1 were disrupted in the presence of Cu2+ ions and this was accompanied by a visible colour change in the solution from colourless to yellow. The addition of lactic acid to the NG1 + Cu2+ solution, on the other hand, induced re-aggregation to fibrillar structures and the colour of the solution again changed to colourless. Hence, it may be surmised that the disaggregation and re-aggregation impart unique dual-sensing properties to NG1 for the sequential detection of Cu2+ ions and lactic acid. The application of NG1 as a selective sensor for Cu2+ ions and lactic acid has been assessed in detail by UV-visible and fluorescence spectroscopy. Furthermore, two structural variants of NG1, namely, NG2 and NG3, were synthesized, which suggest the crucial role of pyridine in imparting panchromatic emission properties and of both pyridine and acyl-thiourea side chain in the binding of Cu2+ ions. The O-methoxy group plays an important part in making NG1 the most sensitive probe of its structural analogs. Finally, the utility of NG1 for the sequential and cellular detection of Cu2+ ions and lactic acid was studied in human RPE cells. The experimental results of the interaction of NG1 with Cu2+ ions and lactic acid have also been validated theoretically by using quantum chemical calculations based on density functional theory (DFT). To the best of our knowledge, this is the first report wherein a dual sensor for Cu2+ ions and lactate ions is synthesized. More importantly, the aggregation properties of the sensor have been studied extensively and an interesting correlation of the photophysical properties of the probe with its self-assembling behavior has been elucidated.

Hybrid Structure of Ionic Liquid and TiO2 Nanoclusters for Efficient Hydrogen Evolution Reaction.

Hydrogen energy has received significant attention in the renewable energy sector due to its high energy density and environmentally friendly nature. For the efficient hydrogen generation from water, the hydrogen evolution reaction (HER) has to be optimized, which requires a highly efficient electrocatalyst. In this work, a hybrid structure of the ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (C2mim TfO) and (TiO2)n nanoclusters with n = 2-12 has been investigated in the pursuit of new catalyst materials for effective HER. We have employed state-of-the-art density functional theory (DFT) computations to depict the HER catalytic performance of IL/(TiO2)n hybrid systems through Gibbs free energy (ΔG) and an exchange-current-based "volcano" plot. We have explored the effect of the TiO2 nanoclusters on the structural and electronic characteristics of the IL, calculating the adsorption energy, the energies of the highest occupied (HOMO) and lowest unoccupied molecular orbitals (LUMO), the HOMO-LUMO band gap Eg, and the work function ϕ. The variation in size of the TiO2 nanocluster in the IL/(TiO2)n hybrid system was found to have a significant influence on the electronic properties. The obtained results suggest that the ΔG of the hydrogen adsorption is remarkably close to the ideal value (0 eV) for the IL/(TiO2)5 system, which also reflects from the volcano plot, suggesting that this complex is the best HER catalyst among the studied systems; it might be even better than the traditional Pt-based catalyst. Thus, the present work suggests ways for the experimental realization of low-cost and multifunctional IL-based hybrid catalysts for clean and renewable hydrogen energy production.

Strong-field ionization of polyatomic molecules: ultrafast H atom migration and bond formation in the photodissociation of CH3OH.

Strong-field ionization induces various complex phenomena like bond breaking, intramolecular hydrogen migration, and bond association in polyatomic molecules. The H-atom migration and bond formation in CH3OH induced by intense femtosecond laser pulses are investigated using a Velocity Map Imaging (VMI) spectrometer. Various laser parameters like intensity (1.5 × 1013 W cm-2-12.5 × 1013 W cm-2), pulse duration (29 fs and 195 fs), wavelength (800 nm and 1300 nm), and polarization (linear and circular) can serve as a quantum control for hydrogen migration and the yield of Hn+ (n = 1-3) ions which have been observed in this study. Further, in order to understand the ejection mechanism of the hydrogen molecular ions H2+ and H3+ from singly-ionized CH3OH, quantum chemical calculations were employed. The dissociation processes of CH3OH+ occurring by four dissociative channels to form CHO+ + H3, H3+ + CHO, CH2+ + H2O, and H2O+ + CH2 are studied. Using the combined approach of experiments and theory, we have successfully explained the mechanism of intramolecular hydrogen migration and predicted the dissociative channels of singly-ionized CH3OH.

Fungal Endophytes as Efficient Sources of Plant-Derived Bioactive Compounds and Their Prospective Applications in Natural Product Drug Discovery: Insights, Avenues, and Challenges.

Fungal endophytes are well-established sources of biologically active natural compounds with many producing pharmacologically valuable specific plant-derived products. This review details typical plant-derived medicinal compounds of several classes, including alkaloids, coumarins, flavonoids, glycosides, lignans, phenylpropanoids, quinones, saponins, terpenoids, and xanthones that are produced by endophytic fungi. This review covers the studies carried out since the first report of taxol biosynthesis by endophytic Taxomyces andreanae in 1993 up to mid-2020. The article also highlights the prospects of endophyte-dependent biosynthesis of such plant-derived pharmacologically active compounds and the bottlenecks in the commercialization of this novel approach in the area of drug discovery. After recent updates in the field of 'omics' and 'one strain many compounds' (OSMAC) approach, fungal endophytes have emerged as strong unconventional source of such prized products.

Rashba Splitting in Two Dimensional Hybrid Perovskite Materials for High Efficient Solar and Heat Energy Harvesting.

The physical properties of two-dimensional (2D) lead halide based hybrid perovskites are quite exciting and challenging. Further, the role of organic cations in 2D perovskites is still in a debate. We investigated layered (CH3(CH2)3NH3)2(CH3NH3)Pb2I7 2D Ruddlesden-Popper (2DRP) phase (M1) and 2D derivative of CH3NH3PbI3 (M2) using density functional theory. The spin orbit coupling mediates the significantly large Rashba splitting energy of 328.5 meV for M2, which is higher than earlier 2D hybrid perovskites. At the picosecond time scale, the dynamical Rashba effect was observed due to organic and inorganic cation dynamics. Two step absorption suggests an indirect optical gap of 2.38 and 2.15 eV for M1 and M2, respectively and solar performance depicts excellent power conversion efficiency of 14.92% and 19.75% for M1 and M2, respectively. For the first time, we explored the thermoelectric properties of 2D hybrid perovskites and perceived high power factor for p-type doping in M2. Our findings suggest that these novel 2D perovskites have the potential to be used in solar and heat energy harvesting.

Impact of alkyl chain length and water on the structure and properties of 1-alkyl-3-methylimidazolium chloride ionic liquids.

The influence of the length of the alkyl chain and water molecules on the hydrogen-bond interaction of the chloride anion and imidazolium-based cation of the ionic liquid (IL) Cnmim Cl (where n = 2, 4, 6, 8, and 10) was investigated by combining attenuated total internal reflection infrared (ATR-IR) spectroscopy and density functional theory (DFT) calculations. Here, for the first time, the conformational isomerism of the alkyl chain of Cnmim Cl (n = 2, 4, 6, 8, and 10) is identified by marker IR bands. The IR peak at 1470 cm-1 related to the alkyl chain vibration exhibits a significant perturbation in its intensity and further shows a red shift upon increasing alkyl chain length. This indeed might be a marker IR band for conformational isomerism and also an indication of the interaction of the alkyl chain with the chloride anion. Further, in the C-H vibration region of the IR spectra, a significant variation of the IR intensities was observed for the νs(CH2) and νas(CH2-CH3) modes at 2931 and 2976 cm-1, respectively. These bands can be considered as further markers for conformational isomerism of the alkyl chain. Moreover, the peak at 2976 cm-1 assigned to an alkyl chain vibration reveals the maximum red shift of 20 cm-1 for n = 10, which suggests charge redistribution among ion-pairs as a result of the alkyl chain variations. Noticeably, the C2-H vibration does not show any significant change of its wavenumber position, suggesting that the alkyl chain length does not interfere with the hydrogen bond interaction between C2-H and the Cl anion. This was also evident from the DFT-calculated bond strength between C2-H and Cl, which remains unchanged upon varying the alkyl chain length. In aqueous solutions, blue shifts of the v(C2-H) band by +65, +60, +67, +62 and +62 cm-1 for Cnmim Cl (n = 2, 4, 6, 8, and 10) are observed, respectively. These results point to a weakening of the hydrogen bond between cation and anion, which is also supported and validated by results of the solvent (water) effect obtained using the polarized continuum model (PCM) of the DFT calculations.

Harnessing the Phytotherapeutic Treasure Troves of the Ancient Medicinal Plant Azadirachta indica (Neem) and Associated Endophytic Microorganisms.

Azadirachta indica, commonly known as neem, is an evergreen tree of the tropics and sub-tropics native to the Indian subcontinent with demonstrated ethnomedicinal value and importance in agriculture as well as in the pharmaceutical industry. This ancient medicinal tree, often called the "wonder tree", is regarded as a chemical factory of diverse and complex compounds with a plethora of structural scaffolds that is very difficult to mimic by chemical synthesis. Such multifaceted chemical diversity leads to a fantastic repertoire of functional traits, encompassing a wide variety of biological activity and unique modes of action against specific and generalist pathogens and pests. Until now, more than 400 compounds have been isolated from different parts of neem including important bioactive secondary metabolites such as azadirachtin, nimbidin, nimbin, nimbolide, gedunin, and many more. In addition to its insecticidal property, the plant is also known for antimicrobial, antimalarial, antiviral, anti-inflammatory, analgesic, antipyretic, hypoglycaemic, antiulcer, antifertility, anticarcinogenic, hepatoprotective, antioxidant, anxiolytic, molluscicidal, acaricidal, and antifilarial properties. Notwithstanding the chemical and biological virtuosity of neem, it has also been extensively explored for associated microorganisms, especially a class of mutualists called endophytic microorganisms (or endophytes). More than 30 compounds, including neem "mimetic" compounds, have been reported from endophytes harbored in the neem trees in different ecological niches. In this review, we provide an informative and in-depth overview of the topic that can serve as a point of reference for an understanding of the functions and applications of a medicinal plant such as neem, including associated endophytes, within the overall theme of phytopathology. Our review further exemplifies the already-noted current surge of interest in plant and microbial natural products for implications both within the ecological and clinical settings, for a more secure and sustainable future.

Impact of Size and Electronegativity of Halide Anions on Hydrogen Bonds and Properties of 1-Ethyl-3-methylimidazolium-Based Ionic Liquids.

The effect of the anion size and electronegativity of halide-based anions (Cl-, Br-, I-, and BF4-) on the interionic interaction in 1-ethyl-3-methylimidazolium-based ionic liquids (ILs) C2mim X (X = Cl, Br, I, and BF4) is studied by a combined approach of experiments (Raman, IR, UV-vis spectroscopy) and quantum chemical calculations. The fingerprint region of the Raman spectra of these C2mim X ion-pairs provides evidence of the presence of the conformational isomerism in the alkyl chain of the C2mim+ cation. The Raman and IR bands of the imidazolium C2-H stretch vibration for C2mim X (X = Cl, Br, I, and BF4) were noticeably blue-shifted with the systematic change in size of anions and the electronegativity. The observed blue shift in the C2-H stretch vibration follows the order C2mim BF4 > C2mim I > C2mim Br > C2mim Cl, which essentially indicates the strong hydrogen bonding in the C2mim Cl ion-pair. DFT calculations predict at least four configurations for the cation-anion interaction. On the basis of relative optimized energies and basis-set-superposition-error (BSSE) corrected binding energies for all ion-pair configurations, the most active site for the anion interaction was found at the C2H position of the cation. Besides information about the C2H position, our DFT results give insights into the anion interaction with the ethyl and methyl chain of the cation, which was also confirmed experimentally [ Chem. Commun. 2015 , 51 , 3193 ]. The anion interaction at the C2H site of the cation favors a planar geometry in C2mim X for X = Cl, Br, and I; however, for BF4, the system prefers a nonplanar geometry where the anion is located over the imidazolium ring. TD-DFT results were used to analyze the observed UV-vis absorption spectra in a more adequate way giving insights into the electronic structure of the ILs. Overall, a reasonable correlation between the observed and the DFT-predicted results is established.

Interplay of Different Moieties in the Binary System 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate/Water Studied by Raman Spectroscopy and Density Functional Theory Calculations.

The present work reports new insights into specific interactions in aqueous solutions of the ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (C2mimTfO). A systematic investigation based on a combination of Raman spectroscopy and density functional theory (DFT) calculations shows evidence of self-encapsulation of the ionic moiety. Raman spectroscopy reveals preferred interactions between water molecules and the TfO- anions. The comparison of the experimental results with dispersion-corrected DFT calculations, which yield the predictions of the possible conformers of the cation-water, anion-water, and cation-anion-water structures, strongly supports the hypotheses of site-selective IL/water interactions. The obtained results allow for a detailed discussion of the nature and strength of the molecular interactions. It is shown that the TfO- anion establishes a preferred interaction with water, whereas the vibrational band at 3118 cm-1 for C-H motion at the C(2) position, the most acidic site for cation and anion interaction, does not indicate any specific energy shift, when adding water to the IL. This finding gives evidence for a self-protective microstructure of the molecules of C2mimTfO in an aqueous environment. In contrast to other ILs reported in the literature, there is no evidence of an increasing cation-anion distance in the IL ion-pair when increasing the water content. Instead, the C2mimTfO molecules undergo a perfect rearrangement, allowing interactions at other molecular sites with higher selectivity. A direct exposure to water at the cation-anion interacting site (C(2) position) is avoided. Ultimately, we show that clusters of ion-pair dimers solvated with water exhibit a more stable geometry compared to the hydrated single ion-pairs, and our calculations correctly reproduce the experimental findings.

Multimodality imaging of vaginal rhabdomyosarcoma.

Rhabdomyosarcoma (RMS) is a malignant mesenchymal tumor arising from the embryonal muscle cells (rhabdomyoblasts), and is the most common soft tissue sarcoma in children and young adults accounting for 4-6% of all malignancies in this age group. Though rare overall, embryonal rhabdomyosarcoma is the most common malignancy arising in the pediatric female genitourinary tract with sarcoma botryoides being the most common variant of the tumor. In young and adolescent individuals, the cervix and uterus are affected; whereas in infants, vaginal lesions are more common. Imaging plays a crucial role not only in the initial diagnosis but also in long-term follow-up of genital RMS. We describe a rare case of embryonal rhabdomyosarcoma of the vagina occurring in a 23-year-old female who presented with abnormal vaginal bleeding ever since she was a child.

Induction of Cryptic and Bioactive Metabolites through Natural Dietary Components in an Endophytic Fungus Colletotrichum gloeosporioides (Penz.) Sacc.

Grape skin and turmeric extracts having the major components resveratrol and curcumin, respectively, were used for the induction of cryptic and bioactive metabolites in an endophytic fungus Colletotrichum gloeosporioides isolated from Syzygium cumini. The increase in total amount of crude compounds in grape skin and turmeric extract treated cultures was 272.48 and 174.32%, respectively, compared to the untreated control. Among six human pathogenic bacteria tested, the maximum inhibitory activity was found against Aeromonas hydrophila IMS/GN11 while no inhibitory activity was observed against Enterococcus faecalis IMS/GN7. The crude compounds derived from turmeric extract treated cultures showed the highest DPPH free radicals scavenging activity (86.46% inhibition) followed by compounds from grape skin treated cultures (11.80% inhibition) and the control cultures (1.92% inhibition). Both the treatments significantly (p ≤ 0.05) increased the antibacterial and antioxidant activities of crude metabolites compared to the control. HPLC profiling of crude compounds derived from grape skin and turmeric extract treated cultures revealed the presence of additional 20 and 14 cryptic compounds, respectively, compared to the control. These findings advocate the future use of such dietary components in induced production of cryptic and bioactive metabolites.

Diversity of endophytic mycobiota of tropical tree Tectona grandis Linn.f.: Spatiotemporal and tissue type effects.

Fungal endophytes were isolated from leaf, bark and stem of Tectona grandis Linn.f. sampled at four geographical locations in winter, summer and monsoon seasons. The recovered 5089 isolates were assigned to 45 distinct morphotypes based on morphology. The sequences of the internal transcribed spacers (ITS) of the nrDNA of some morphotypes were identical, but morphological differences were strong enough to consider these morphotypes as separate species. Forty-three morphotypes were assigned to ascomycotina and two to basidiomycotina. Ascomycotina was the predominating group with 99.7% of total isolates followed by basidiomycotina with only 0.3% of total isolates. Diaporthe (Phomopsis) species dominated the communities independently on tissue type, location or season. More than 60% of the examined tissue pieces were colonized by members of this species complex. While these endophytes are ubiquitous others were tissue or location specific. Tissue type had the strongest effect on the species evenness of the endophytic assemblage followed by geographical location and season. However, Shannon-Wiener index (H') significantly (p ≤ 0.001) varied with all three factors i.e. season, location and tissue type. Leaves supported the highest diversity across all the seasons and locations. In conclusion, all the three factors together determined the structure of endophytic mycobiota assemblage of T. grandis.

Molecular Structure and Interactions in the Ionic Liquid 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate.

Quantum chemical theory (DFT and MP2) and vibrational spectroscopy (ATR-IR and Raman) were employed to investigate the electronic structure and molecular interactions in the room-temperature ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate. Various possible conformers of a cation-anion pair based on their molecular interactions were simulated in the gas phase. All the different theoretical (MP2, B3LYP, and the dispersion-corrected wB97XD) methods assume the same ion-pair conformation for the lowest energy state. Basis set superimpose error (BSSE) correction was also introduced by using the counterpoise method. Strong C-H···O interactions between the most acidic hydrogen atom of the cation imidazole ring (C2H) and the oxygen atom of the anion were predicted where the anion is located at the top of (C2H). In this case, methyl and alkyl groups also interact with the anion in the form of a C-H···O hydrogen bond. Interestingly, the dispersion-corrected methodology neglects the C4/C5-H···O and C-H···F interaction in the ion-pair calculations. The theoretical results were compared with the experimental observations from Raman scattering and ATR-IR absorption spectroscopy, and the predictions of the molecular interactions in the vibrational spectra were discussed. The wavenumber shifts of the characteristic vibrations relative to the free cation and anion are explained by estimating the geometric parameters as well as the difference in the natural bond orbital (NBO) charge density.